Silylhydrocarbyl phosphine transition metal complexes

ABSTRACT

Novel heterogeneous silylhydrocarbyl phosphine transition metal complex catalysts and intermediates therefor are prepared by (a) the selective monoaddition of silane having chlorine, alkoxy or acyloxy groups to an α,ω-diene, (b) followed by the addition of a phosphine to the resulting ω-alkenyl silanes to form the corresponding silylalkyl phosphines, (c) which are then covalently anchored as such or in the form of their transition metal complexes via condensation of their reactive silane substituents with hydroxy groups of silica and metal oxides, (d) optionally followed by complexing the free phosphine groups of anchored silylalkyl phosphines with transition metal compounds.

CROSS-REFERENCE TO RELATED CASES

This application is a continuation-in-part of Ser. No. 601,628, filedSept. 5, 1975, now U.S. Pat. No. 4,083,803 which is acontinuation-in-part of Ser. No. 265,507, filed June 23, 1972, now U.S.Pat. No. 3,907,852.

This invention relates to a novel method of anchoring phosphinecomplexes of transition metals to inorganic solids such as silica forthe production of novel catalysts.

The novel method of anchoring is based on the known ability of certainsilane compounds to react with the hydroxyl groups of silica and thelike (see Plastic Report 18 entitled "Glass/Resin Interface: PatentSurvey, Patent List, and General Bibliography", Office of TechnicalServices, Department of Commerce). The complexing reactions of simplehydrocarbon phosphines with transition metals are also known as well asthe use of such complexes in catalysis. (For reference see the monographof Juergen Falbe, "Carbon Monoxide in Organic Synthesis",Springer-Verlag, New York, 1970.)

The present invention chemically links the reactive silane group and thecomplex forming phosphine group via a divalent hydrocarbon radical. Suchbridged silaphosphines are then anchored and complexed with transitionmetals to derive new types of catalysts. These catalysts are insolubleand as such, are free from the catalyst recovery problems commonlyexperienced with the known soluble complexes of phosphines.

The present invention is most closely related to U.S. Pat. No. 3,726,809on "Catalyst Supports and Transition Metal Catalysts Supported Thereon"by K. G. Allum, S. McKenzie and R. C. Pitkethly. This patent disclosed asimilar approach to catalyst anchoring. However, the only catalystligand used for anchoring by Allum et al, is 2-triethoxysilylethyldiphenyl phosphine, a known compound:

    (C.sub.6 H.sub.5).sub.2 PCH.sub.2 CH.sub.2 Si)(OC.sub.2 H.sub.5) .sub.3

other known silylalkylphosphines which may be represented by the generalformula: ##STR1## wherein R is phenyl, ethyl, butyl, R₁ is ethoxy,methyl, phenyl and (R₂)₂ is ethoxy, chlorine and n is 2 and 3, aredescribed as exemplary anchoring ligands on column 4, lines 4 to 26 ofthe same patent. All these phosphines have an alkylene bridge having twoor three carbon atoms between the silicon and phosphorus.

In the generic disclosure in claim 3 of the Allum et al patent compoundsof the formula: ##STR2## wherein R₁ and R₂ are selected from the groupconsisting of aryl, alkyl, alkoxy and aryloxy groups containing up to 10carbons, and halogen, R₃ and R₄ are selected from the group consistingof aryl and alkyl groups containing up to 10 carbon atoms, R₅ isselected from the group consisting of halogen, alkoxy and aryloxycontaining up to 10 carbon atoms and n is an integer of from 1 to 6, arepresented as possible anchoring compounds. However, in all the workingexamples and in the description at Column 4, lines 65 to 75 of the U.S.patent, the alkylene bridge between phosphorus and silicon has two orthree carbons.

In contrast, the key to the present invention is the synthesis of novelsilylalkylphosphine anchoring agents via novel olefinic silanes with newmethods. The most important, distinctive property of these novelanchoring agents, hitherto unavailable via known processes, is thelonger alkylene bridge connecting the phosphine and silicon moiety.These anchoring agents were converted to anchored transition metalcomplexes which were found to be superior selective catalysts in thepresent invention. Such anchored catalysts are also superior to similartransition metal complex catalysts anchored to organic polymers, e.g.macroreticular resins. The superiority of the present catalysts islargely due to the stability and the high surface to weight ratio of theinorganic solids they are attached to.

In the subsequent detailed discussion of our invention, the synthesis ofsubstituted silylalkylphosphine anchoring agents via silane-dienemonoaddition followed by phosphine addition will be considered at first.Anchoring reactions with silica and the like and complexing withtransition metals will be described thereafter. Finally, novel processesusing the anchored catalysts will be discussed. For the details of someof the working examples, reference is made to the parent application,U.S. Ser. No. 265,507.

1. Addition of Silanes to the α,ω-Dienes

The addition of silanes, containing the reactive Si-H functionality, tomonoolefins is well known. For reference, see the monograph by C. Eabornentitled "Organosilicon Compounds", Academic Press, New York, 1970,pages 45-64. However, the addition of silanes to α,ω-dienes iscomplicated by the tendency of terminal vinylic groups to isomerize intointernal olefinic groups during the addition.

It was found in the present invention that chlorosilanes can be addedselectively to α,ω-dienes in a selective terminal manner to yield novelω-alkenyl silane monoadducts and bis-α,ω-silyl alkanes.

The silane reactants are preferably of the general formula:

    R.sub.4-y SiH.sub.y

wherein R is chlorine; C₁ to C₄ alkoxy such as methoxy, ethoxy, propoxy;C₁ to C₄ acyloxy such as acetoxy; R can also be a C₁ to C₆ saturatedaliphatic or aromatic hydrocarbyl such as phenyl, methyl providing thatat least one of the R groups is a reactive chlorine, alkoxy or acyloxygroup; y is 1 and 2. The reactive R is preferably chlorine or acyloxy,most preferably chlorine. It is preferred that all R groups be reactive.

The α,ω-diene reactants of the present invention are of the generalformula:

    CH.sub.2═ CH(CH.sub.2).sub.k CH═CH.sub.2

wherein k is 1 to 26, preferably 4 to 26, more preferably 4 to 10, mostpreferably 6 to 10.

Exemplary reactants are trichlorosilane, triethoxysilane,triacetoxysilane, methyldichlorosilane, phenylchlorosilane,1,4-pentadiene, 1,21-docosadiene, 1,13-tetradecadiene.

It was found that these reactants yield selectively ω-alkenyl silanesand bis α,ω-silyl alkanes according to the following schemes:

    R.sub.4-y SiH.sub.y + CH.sub.2 ═CH(CH.sub.2).sub.k CH═CH.sub.2 → R.sub.4-y Si[ (CH.sub.2).sub.1 CH═CH.sub.2 ].sub.y

wherein y is 1 and 2 and 1 is k + 2 and ##STR3## wherein m is k + 4.

Such additions are preferably carried out in the liquid phase in thepresence of free radical and/or metal and/or metal salt catalysts.Exemplary free radical catalysts are radiation such as ultraviolet lightand gamma rays, chemicals such as peroxide compounds and azo compoundsand thermal catalysis by heating. Exemplary metal catalysts are forexample, platinum, palladium, usually on either asbestos or alumina orcharcoal. Illustrations for metal salt catalysts are potassiumchloroplatinate, chloroplatinic acid, ruthenium chloride. These metalsalts can be also used as their complexes, for example withtrihydrocarbyl phosphines.

The temperature of these additions may vary from -90° C. to 200°,preferably -90 to 90° C., most preferably from -90 to 30° C. Thetemperature may be critical with regard to selective monoaddition toyield ω-alkenyl silanes.

The ratio of the reactants may vary from 0.5 to 6 moles of diolefin permole of silane. It is, however, preferred for a selective monoadditionto use 2 to 6 moles of diolefin per mole of silane.

The additions are carried out to a substantial conversion and theproducts are then isolated usually by fractional distillation.

The ω-alkenyl silane monoadducts have properties unexpectedly differentfrom the known vinyl and allyl silanes of analogous structure. Thechloro derivatives are more reactive in Ziegler-type polymerization.These terminally unsaturated compounds behave also very differently fromtheir internally unsaturated isomers. The terminal olefinic group ofthese compounds, for example, is reactive towards phosphine addingagents while the internal compounds are inert.

The bis-α, ω-silyl alkanes are useful as crosslinking reagents due totheir diterminal functionality. As such they may find particularapplications in adhesives, mastics and the like.

2. Addition of Phosphines to Alkenyl Silanes

The addition of phosphines to vinylsilanes has been extensively studiedby H. Niebergall. (See Makromolekulcare Chemie, Volume 52, pages218-229, which was published in 1962). He has found that diethylphosphine reacts with divinyl dichlorosilane as shown by the followingreaction schemes: ##STR4## Niebergall reported that both of the abovereactions occur under free radical conditions.

In the present work, it was surprisingly found that in the reaction ofphosphines with ω-alkenyl silanes, the formation of P--Si bonds can beavoided. As such the reaction could be used, preferably under mildconditions, for the synthesis of novel ω-silylalkyl phosphines.

The phosphine adding agent is of the general formula:

    R'.sub.3 -x PH.sub.x

wherein R' is a C₁ to C₃₀ saturated aliphatic or aromatic hydrocarbylradical selected from the group consisting of alkyl, cycloalkyl,phenylalkyl, phenyl, alkylphenyl. R' is preferably C₁ to C₃₀ alkyl,cyclohexyl and phenyl, most preferably C₁ to C₄ alkyl, cyclohexyl andphenyl. The symbol x stands for numbers 1-3, preferably 1-2.

The ω-alkenyl silane reactants are of the general formula:

    (R.sub.4-y Si[(CH.sub.2).sub.1 CH═CH.sub.2 ].sub.y

wherein the meaning of the symbols is the same as in part 1. of thedisclosure.

The reaction of the above phosphines with the ω-alkenyl silanesaccording to the present invention involves only the P--H and CH₂═CH--Si groups as shown by the following reaction equation: ##STR5##wherein the meaning of old symbols is the same as before. The new symbolz is a number from 1-3. The value of z is, of course, selected so as tosatisfy the valence relationships.

Preferred additions and compositions are those wherein x and y are 1 and2, for example ##STR6##

Specifically preferred are ω-alkenyl chlorosilane and acyloxysilanereactants and compositions resulting therefrom, e.g.

    R'.sub.2 PH + CH.sub.2 ═CH(CH.sub.2).sub.1 SiCl.sub.3 → R.sub.2 P(CH.sub.2).sub.m SiCl.sub.3

The desired anti-Markovnikov-type reaction is initiated by the use offree radical catalysts such as radiation and/or chemical initiators.Initiation by radiation includes gamma rays and ultraviolet light.Typical chemical initiators are azo compounds such asazo-bis-isobutyronitrile. The use of irradiation and its combinationwith chemical initiation are preferred over the use of chemicalinitiation alone. Radiation means of initiation allow the use of lowreaction temperatures.

The temperature of the reaction is between -105° and +100° C.,preferably between -100 and +16° C., most preferably between -80° C. and0° C. The highest allowed reaction temperature is largely dependent onthe basicity of the phosphine used. The more basic dialkyl phosphineshave a higher tendency to undergo undesirable side reactions involvingthe chlorosilane groups.

The reaction is to be carried out in the liquid state. This means thatthe process is normally atmospheric. In the case of phosphines which arenormally gaseous at the reaction temperature, such as methylphosphine,superatmospheric pressures up to 20 atmospheres may be used to keep thereactants in the liquid phase.

The reaction is usually carried out without added solvents. At times,however, nonreactive solvents can be advantageously used. Preferredsolvents include ketones such as methyl ethyl ketone, ethers andthio-ethers such as dipropyl sulfide, aliphatic and cycloaliphatichydrocarbons such as cyclohexane, aromatic hydrocarbons and theirhalogenated derivatives such as chlorobenzene.

The ratio of reactants is not critical. The reactants are usuallyemployed in equivalent quantities. However, it is preferred to have 0.3to 6 moles of phosphine per mole of alkenyl silane. In the case ofmonofunctional reactants, the use of 1.5 to 2.5 mole of phosphine permole of alkenyl silane is preferred.

The addition reactions are preferably run to a 20 to 90% conversion ofthe phosphine. The preferred conversion is in excess of 50%. Highreactant conversions can be important for avoiding undesired sidereactions. At the completion of the reaction, the unreacted componentsare removed, usually by vacuum stripping. The products can be purified,preferably by fractional distillation in vacuo.

3. Silyhydrocarbyl Phosphine - Transition Metal Complexes

It was found in the present invention that transition metal saltscomplex with silylhydrocarbyl phosphines of the general formula:

    (R'.sub.3-x P).sub.z Q.sub.y SiR.sub.4-y

wherein Q is C₅ to C₃₀, preferably C₈ -C₃₀, saturated aliphatic oraromatic hydrocarbylene such as phenylene, xylylene, terphenylene,preferably (CH₂)_(p) with p being 5-30, more preferably p equals 8-30,preferably 8 to 14. The meaning of the other symbols is the same aslisted in the previous part of this specification. In effect, one of thepreferred formula of the silylhydrocarbyl phosphines is as listed there

    (R'.sub.3-x P).sub.z [(CH.sub.2).sub.m ].sub.y SiR.sub.4-y

Compounds of the above and similar more preferred formula react withtransition metal compounds such as those of Groups VI, VII and VIII,e.g. of Fe, Ru, Os, Rh, Ir, Ni, Co, Pd and Pt of the formula

    MX.sub.n

wherein M is the metal, X is an anion or organic ligand which satisfiesthe coordination sites of the metal; n is 2 to 6.

Important anions or organic ligands are enumerated in the followinglist. This list is presented solely by way of example and is not to betaken as a definitive or complete listing of all usable anions ororganic ligands. Those skilled in the art with the teaching before themwill have no difficulty in selecting other anions or organic ligands notlisted which will function in the instant invention.

Anions for Organic Ligands

H⁻, alkyl⁻, aryl⁻ substituted aryl⁻, F⁻, CF₃ ⁻, C₂ F₅ ⁻ etc., Cl⁻, CCl₃⁻, Br⁻, I⁻, CN⁻, OCN⁻, SCN⁻, SeCN⁻, SeSN₃ ⁻, N₃ ⁻, C(O)R⁻ where R isalkyl or aryl, acetate, acetylacetonate, SO₃ ⁻, SO₄ ⁼, PF₄ ⁻, NO₂ ⁻, NO₃⁻, O₂ ⁻, OMe⁻, OEt⁻, alkoxy, allylic anions such as C₃ H₅, phosphines,phosphine oxides, CO, C₆ H₅ CN, CH₃ CN, EtCN, PrCN, NO, NH₃, pyridine,amines such as N(CH₃)₃, HN(CH₃)₂, N(Et)₃ chelating amines such as N(CH₃CH₂ NMe₂)₃, chelating olefins and di and tri olefins, H₂ O, ethers,ketones, alcohols, anchoring ligands such as PF₂ C*, P(CF₃)₂ C* (where *indicates an optically active center), chelating phosphines such asCl.sub. 2 Si[(CH₂)_(x) PMN]₂ (MeO)₂ Si[(CH₂)_(x) PMN]₂ etc. wherein Mand N are selected from the group consisting of alkyl, aryl,fluoroalkyl, substituted aryl, etc. ClSi[(CH₂)_(x) PMN]₃ MeOSi[(CH₂)_(x)PMN]₃ wherein M and N are as previously defined, ligands containing anoptically active phosphorous center such as:

    (C.sub.6 H.sub.5)--R'--P*--E, (C.sub.6 H.sub.11)--R'--P*--E,

r"p*--e, wherein R' is selected from the group consisting of C₁ to C₆straight and branched chain alkyls and R" is selected from the groupconsisting of C₃ -C₆ straight or branched chain alkyl, E is selectedfrom the group consisting of ##STR7## anchoring bridge wherein X isselected from the group consisting of Cl, Br, F, I, etc. and x is anumber ranging from 1 to 30.

Preferred metal compounds contain a readily displaceable organic ligandsuch as carbonyl, monoolefin, diolefin, tetrahydrofuran, pyridine,acetonitrile. Other preferred metal compounds are capable of raisingtheir coordination number, e.g. nickel-1,5,9-cyclododecatriene.Preferred anions include chlorine, bromine or acetate.

In a most general way, the novel silylhydrocarbyl phosphine-transitionmetal complexes can be defined by the following formula: [(R'_(3--x)P)_(z) Q_(y) SiR_(4-y) ]_(g) •(MX_(n))_(s) wherein g is 1 to 6, s is1-3.

For the purposes of discussing the metal complex formation withsilylhydrocarbyl phosphines, compounds having x, y, z equal 1 areselected for illustration, e.g.

    R'.sub.2 PQSiR.sub.3 and R'.sub.2 P(CH.sub.2).sub.m SiR.sub.3

these compounds and the like are designated L, as monophosphines of aparticular structure.

The transition metal complexes may contain various numbers of phosphineligands as indicated by the formula:

    L.sub.r •MX.sub.n

wherein n and r are 1-6 providing that n + r is 2 to 6, preferably 4.

A preferred example of these metal complexes can be formed fromdiene-rhodium chloride complex dimers such as that of 1,5-cyclooctadienei.e. 1,5-COD: ##STR8##

As indicated by the above scheme, the structure of the complexes isdependent on the ratio of the reactants. In general, no reactant is tobe used above the stoichiometric quantity.

The complexing reactions are usually dependent on the temperature used.Of course, the practical temperatures are below the decompositiontemperature of the complex formed. The temperature is preferably in therange of -90 to 200° C.

The reactions are preferably carried out in the liquid phase in thepresence of inert solvents. Hydrocarbons such as paraffins, aromaticsand their chlorinated derivatives may be used. Ethers such astetrahydrofuran can be also suitable. Reactions using volatiletransition metal compounds such as nickel tetracarbonyl can be alsocarried out in the vapor phase.

The novel complexes are usually soluble in hydrocarbons and can be usedin solutions. However, they can be also isolated by crystallization orthe removal of the solvent by distillation.

4. Anchoring of Silylhydrocarbyl Phosphines and Transition MetalComplexes Thereof

The novel phosphine ligands of the present invention and their metalsalt complexes can be reacted with the hydroxyl groups of solid,insoluble inorganic compositions, such as those present on the surfaceof dehydrated silica and metal oxides, e.g. titanium oxide and aluminumoxide. These hydroxyl groups may be covalently bound to silicon oraluminum or may come from coordinatively bound surface water. Whatevertheir exact bonding may be, reaction of these hydroxyl groups with thechlorosilane groups of the phosphine ligand occurs with the formation ofHCl.

Materials which contain or can be made to contain free silanol, i.e.Si--OH groups include various forms of diatomaceous earth, e.g. the wellknown chromosorbs in gas liquid chromatography, silica gels, silicabeads, glass beads.

The anchoring reactions of the reactive silane functions of the presentphosphines establish a silicon oxygen bond as indicated by the followingschemes: ##STR9## wherein R" is a C₁₋₄ alkyl and R"' is a C₁₋₃ alkyl orhydrogen. R"' is most preferably methyl.

Since the silyl groups of our phosphines may contain 1 to 3 of the abovereactive groups, more than one of them may react per molecule.Concurrent with the anchoring or preferably subsequently some of thesereactive groups may be hydrolyzed by water which converts them tosilanol groups. The latter may undergo siloxane type condensation, e.g.

    2 Si--OH → Si--O--Si + H.sub.2 O

the general scheme of anchoring can be depicted by the following scheme:##STR10## wherein t = 0-3.

The anchoring reaction results in the formation of Si--O bonds asillustrated by the following example: ##STR11##

The anchoring reaction can be carried out in a broad temperature rangefrom -50 to +400° C, preferably from -20 to 200° C. In the case ofdehydrated silica it was surprisingly found that anchoring occurs at lowtemperatures in the order of -50 to +50° C.

The anchoring reactant is best applied in a solvent. It can be used byimpregnation onto silica. In the case of dehydrated silica orundehydrated silica, about one silyl group can be anchored per 50 A°² ofthe surface. This corresponds to a complete surface coverage. For thepresent silylhydrocarbyl phosphines, it is preferred to have less thanabout 50% surface coverage in order to derive more effective catalysts.

Under the preferred conditions of the present invention, when anω-trichlorosilylalkyl phosphine is anchored by impregnating silica withits solution in an inert solvent, fewer than three of the chlorine atomsper anchored phosphine group are detached from the silica. The chlorineleft can be subsequently removed by extraction using a reactive solventsuch as boiling methanol. However, it is pointed out that the degree ofprimary chloride elimination from the trichlorosilane group is higher ifthe polymethylene moiety bridged to the phosphine contains a highernumber of carbon atoms.

In the present invention, when silica having 1.5 x 10⁻³ mole equivalentsof silanol per gram is used, about 0.8 × 10⁻³ mole phosphine or itsequivalent phosphine complex was anchored per gram silica. According toa preferred embodiment of the present process, the anchoring is carriedout using 0.8 m mole or less, preferably less phosphine per g. of such asilica. In general, the phosphine is preferably used in equivalent orless amounts to react with the hydroxyl groups of silica or otherinorganic solids. In contrast the earlier referred Allum et al patentused the anchoring phosphine in severalfold excess.

If the anchoring is carried out with the silylhydrocarbyl phosphines,complexing with the transition metal compounds can be carried outsubsequently. The anchored phosphines undergo complex formation withtransition metal compounds in the same manner the non-anchored parentphosphines do. However, it is pointed out that using the anchoredphosphines stable transition metal complexes can be prepared which areotherwise unstable or unavailable. Covalent anchoring of the phosphineto the inorganic support inhibits ligand interchange and allows thesynthesis of novel complexes having a one-to-one phosphine to metalratio. Complexes having a one-to-three ratio were also prepared asexemplified by the following reaction schemes starting with the1,5-cyclooctadiene rhodium chloride dimer and anchored phosphines (L):##STR12## The Allum et al patent described only the preparation ofcomplexed having a two-to-one phosphine rhodium ratio.

5. Properties of Anchored Silyhydrocarbyl Phosphines and TransitionMetal Complexes Thereof.

The anchored phosphines of the present invention may be used in thefield of separations for reversible complexing with acids, metal saltsand the like.

The metal complexes of the anchored phosphines represent a novel type ofcatalysts. These anchored catalysts act in the same manner solubleorganometallic catalysts do. They catalyze the same reactions. However,due to their insolubility our catalysts are suited for continuousoperations. Catalyst losses can be drastically reduced using ouranchored complexes. Another advantage of anchoring resides in thepotentially increased stereo-selectivity of our catalysts. The approachof reactants to the anchored complex catalyst can occur only from thenon-anchored side.

For reference on transition metal phosphine complex catalysts see"Homogeneous Catalysis," No. 70 in the Advances in Chemistry Series ofthe American Chemical Society and a monograph by J. P. Candlin, K. A.Taylor and D. P. Thompson entitled "Reactions of Transition MetalComplexes," Elsevier, N.Y., 1968. Anchored ω-trichlorosilylalkylphosphine-rhodium complexes with different polymethylene chain lengthshave differing catalytic activity. For example, L₃ RhCl complexes whereL represents an anchored phosphine with a dimethylene bridge, is not ahydroformylation catalyst, whereas where L is a C₈ or C₁₄ polymethylenechain, the L₃ RhCl catalyst is an active hydroformylation catalyst.Further, the (1,5-cyclooctadiene)LRhCl complex where L represents ananchored phosphine with dimethylene bridge is also not ahydroformylation catalyst, whereas where L is a C₈ or C₁₄ polymethylenechain, the (1,5-cyclooctadiene)LRhCl complexes are activehydroformylation catalysts.

In the case of trialkyloxy- and triacyloxysilylated phosphines thelength of the polymethylene group similarly influences the catalyticactivity of the anchored phosphines.

The catalytic activity was also dependent on the phosphine coordinationnumber at the metal center, i.e., L to Me ratio, in a selective manner.For example, in the catalysis of hydroformylation reactions, the lowerthe coordination number, the more active the catalyst. In contrast, forhydrogenation anchored complexes having the highest coordination numberhave the maximum activity.

Anchored catalysts particularly palladium complexes were also effectivefor the carbonylation of arylmercury acyloxylates such as thetrifluoroacetate in the presence of alcohol, i.e., methanol, to formaromatic esters, e.g., methyl benzoate.

Anchored catalysts can be repeatedly recycled from a batch catalyticreaction without loss in catalytic activity. For example, L₃ RhCl whereL represents an anchored phosphine with a C₈ methylene chain showed nodecrease in hydrogenation activity after being repeatedly recycled.

It can be concluded that metal loss from these novel heterogeneouscatalysts is not observed under corrosive solvent and severe reactionconditions.

A. Synthesis of Alkenyl Silanes EXAMPLE 1 -- Addition of Trichlorosilaneto 1,7-Octadiene in the Presence of Chloroplatinate ##STR13##

A. To a stirred mixture of 27.1 g (0.2 mole) trichlorosilane and 66 g(0.6 mole) 1,7-octadiene in a round bottom flask, is added 0.1 ml of a10% ethanolic solution of 40% hexachloroplatinic acid. The reactionmixture was heated up to 130° C and kept there for 28 hours to completethe addition. Thereafter, the mixture was fractionally distilled toobtain 49 g, i.e., 70% yield of the 8-octenyl trichlorosilane monoadductas a colorless liquid boiling between 51-53° at 0.3 mm and 6 g of the1,8-bistrichlorosilyloctane diadduct as a distillation residue.Analyses. Calcd. for the monoadduct, C₈ H₁₇ SiCl₃ : C, 39.11; H, 6.16;Cl, 43.35. Found: C, 39.34; H, 5.72; Cl, 42.44. A proton magneticresonance (nmr) spectrum of the product shows the characteristic complexresonance signals of the terminal --CH═CH₂ group.

B. A mixture of 108.4 g (0.8 mole) trichlorosilane and 264 g (2.4 mole)1,7-octadiene was similarly reacted after the addition of 0.4 ml 10 %ethanolic solution of 40% chloroplatinic acid by heating the mixture at50° C for 44 hours. A subsequent fractionation in vacuo yielded 154 g,i.e., 80% of the monoadduct and 20 g, i.e., 10% of the diadduct as acolorless liquid distilling at 123-125° at 0.4 mm pressure.

Analyses: Calcd. for the diadduct, C₈ H₁₆ Si₂ Cl₆ : C, 25.21; H, 4.23;Cl, 55.82. Found: C, 24.71; H, 4.00; Cl, 54.64. An nmr spectrum of theproduct shows only CH₂ absorptions, indicating a straight chainoctamethylene structure.

C. In another experiment, 220 g (1.62 mole) trichlorosilane was addedslowly in 20 minutes to a stirred mixture of 660 g (6 mole)1,7-octadiene at 35° C. Subsequently, the reaction mixture was heated at50° C for 24 hours to complete the addition and then fractionallydistilled. This resulted in 322 g, i.e., 82%, 7-octenyl trichlorosilaneand 24 g, i.e., 12%, 1,8-bis-trichlorosilyl octane.

D. When 0.015 ml of the ethanolic chloroplatinic acid was added to amixture of 3.4 g (0.025 mole) trichlorosilane and 5.5 g (0.05 mole)1,7-octadiene and the reaction mixture heated at 50° C for 18 hours, asimilar addition took place without a double bond isomerization.

E. Similarly, addition without isomerization occurred when the abovereactant mixture was allowed to stand at ambient temperature in thepresence of 0.015 ml added 10% isopropanol solution of 40%chloroplatinic acid as a catalyst.

EXAMPLE 2. -- Addition of Trisubstituted Silanes to α ω Dienes

In a manner, similar to that described in the first example, a number oftrisubstituted silanes were added to a variety of α, ω diolefins (TableI) to obtain the corresponding ω alkenyl and internal silanesmonoadducts shown in Table II and α, ω bis- silylalkanes shown in TableIII. The terminal versus internal position of the double bonds of themonoadducts and the saturated alkylehe structure of the diadducts wereshown by now.

                                      TABLE I                                     __________________________________________________________________________    ω-ALKENYL SILANES BY THE ADDITION OF SILICON HYDRIDES TO α,       ω-DIENES                                                                 ##STR14##                                                                                    Diene per                                                                           Max.  Reaction                                                                           Yield of                                                                             Yield                                 Ref.                                                                              Diene,                                                                            Silane, Silane                                                                              Reaction                                                                            Time,                                                                              Dist'd Mono-                                                                         of Dist'd                             No. n   R.sub.3 SiH                                                                           Mole Ratio                                                                          Temp. ° C.                                                                   Hours                                                                              Adduct, %                                                                            Diadduct                              __________________________________________________________________________    1   4   Cl.sub.3 SiH                                                                          3     130   28   70                                           2       Cl.sub.2 Si(CH.sub.3)H                                                                3     115   <1   70     14                                    3       (C.sub.2 H.sub.5 O).sub.3 SiH                                                         3     50    24   79     10                                    4   2   Cl.sub.3 SiH                                                                          3     50    65   90     4.5                                   5       (C.sub.2 H.sub.5 O).sub.3 SiH                                                         1     50    24   44     39                                    6    2* Cl.sub.3 SiH                                                                          1     55    18   57                                           7       (C.sub.2 H.sub.5 O).sub.3 SiH                                                         1     70    <1    88*                                         8   10  Cl.sub.3 SiH                                                                          2     30     2   41                                           9       Cl.sub.3 SiH                                                                          1     70    <1     70** 30                                    10  6   Cl.sub.3 SiH                                                                          5/3   130        41     10                                    __________________________________________________________________________     *Instead of 1,5-hexadiene, 1,4-hexadiene was used as a starting material.     **The terminal double bond of the adduct was isomerized to an internal        position during the process.                                             

                                      TABLE II                                    __________________________________________________________________________    SOME PHYSICAL AND ANALYTICAL DATA OF SUBSTITUTED ALKENYL SILANES                                         Elemental Composition                              Ref.               Boiling Range                                                                         Calcd.   Found                                     No.                                                                              Chemical Structure                                                                             ° C/mm                                                                        C  H  Cl C  H  Cl                                  __________________________________________________________________________    1  CH.sub.2 =CH(CH.sub.2).sub.6 SiCl.sub.3                                                       51-53/0.3                                                                             39.11                                                                            6.16                                                                             43.35                                                                            39.34                                                                            5.72                                                                             42.44                               2  CH.sub.2 =CH(CH.sub.2).sub.6 Si(CH.sub.3)Cl.sub.2                                             50-52/0.1?                                                                            47.99                                                                            8.05  47.62                                                                            7.82                                   3  CH.sub.2 =CH(CH.sub.2).sub.6 Si(OC.sub.2 H.sub.5).sub.3                                       65-68/0.05                                                                            61.26                                                                            11.02                                                                            -- 61.58                                                                            10.57                                                                            --                                  4  CH.sub.2 =CH(CH.sub.2).sub.6 Si(OCH.sub.3).sub.2 Cl                                           60-62/0.1                                                                             50.72                                                                            10.41 50.50                                                                            9.52                                   5  CH.sub.2 =CH(CH.sub.2).sub.6 Si(OCH.sub.3).sub.3                                              48-49/0.1                                                                             56.85                                                                            10.41                                                                            -- 55.72                                                                            9.53                                                                             --                                  6  CH.sub.2 =CH(CH.sub.2).sub.4 SiCl.sub.3                                                       33-34/0.7                                                                             33.12                                                                            5.10  33.10                                                                            4.74                                   7  CH.sub.3 CH=CH(CH.sub.2).sub.3 SiCl.sub.3                                                     38-39/0.1                                                                             33.12                                                                            5.10                                                                             48.88                                                                            32.51                                                                            4.83                                                                             47.87                               8  CH.sub.2 =CH(CH.sub.2).sub.4 Si(OC.sub.2 H.sub.5).sub.3                                       55-56/0.15                                                                            58.47                                                                            10.64                                                                            -- 58.56                                                                            10.50                                                                            --                                  9  CH.sub.3 CH=CH(CH.sub.2).sub.3 Si(OC.sub.2 H.sub.5).sub.3                                     48-50/0.15                                                                            58.47                                                                            10.64 59.14                                                                            10.12                                  10 CH.sub.2 =CH(CH.sub.2).sub.12 SiCl.sub.3                                                      103-105/0.05                                                                          50.98                                                                            8.25                                                                             32.25                                                                            50.80                                                                            7.80                                   11 n-C.sub.14 H.sub.27 SiCl.sub.3                                                                123-125/0.3                                                                           50.98                                                                            8.25                                                                             32.25                                                                            51.54                                                                            8.31                                                                             33.04                               12 n-C.sub.10 H.sub.19 SiCl.sub.3                                                                73-75/0.2                                                                             43.88                                                                            7.00                                                                             38.86                                                                            44.53                                                                            6.50                                                                             39.16                               __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________    SOME PHYSICAL AND ANALYTICAL DATA OF α. ω-BIS-SUBSTITUTED         SILYL ALKANES                                                                                               Elemental Composition                           Ref.                 Boiling Range                                                                          Calcd.   Found                                  No.  Chemical Structure                                                                             ° C./mm                                                                        C  H  Cl C  H  Cl                               __________________________________________________________________________    1    Cl.sub.3 Si(CH.sub.2).sub.8 SiCl.sub.3                                                        123-125/0.4                                                                            25.21                                                                            4.23                                                                             55.82                                                                            24.71                                                                            4.00                                                                             54.64                            2    Cl.sub.2 Si(CH.sub.3)(CH.sub.2).sub.8 Si(CH.sub.3)Cl.sub.2                                    125-126/0.2                                                                            35.30                                                                            6.52  36.16                                                                            6.44                                3    (C.sub.2 H.sub.5 O).sub.3 Si(CH.sub.2).sub.8 Si)OC.sub.2 H.sub.5).sub         .3              140-141/0.1                                                                            54.75                                                                            10.57                                                                            -- 54.34                                                                            10.47                               4    Cl.sub.3 Si(CH.sub.2).sub.6 SiCl.sub.3                                                        96-98/0.25                                                                             21.2                                                                             3.40  21.20                                                                            3.40                                5    (C.sub. 2 H.sub.5 O).sub.3 Si(CH.sub.2).sub.6 Si)OC.sub.2 H.sub.5).su         b.3             127-128/0.15                                                                           52.64                                                                            10.31                                                                            -- 53.29                                                                            10.21                               6    Cl.sub.3 Si(CH.sub.2).sub.14 SiCl.sub.3                                                       172-175/0.3                                                                            36.14                                                                            6.07                                                                             45.72                                                                            36.75                                                                            5.84                                                                             44.63                            7    Cl.sub.3 Si(CH.sub.2).sub.10 SiCl.sub.3                                                       121-123/0.1                                                                            29.35                                                                            4.93  30.35                                                                            4.69                                __________________________________________________________________________

In general, small concentrations of hexachloroplatinic acid (about 0.05mole %) were found to be effective and selective catalysts for suchreactions at ambient temperatures. The yield of mono- versus diadductscould be increased by using an excess of the diolefin reactant (TableI).

The mono- and diadduct products are, in general, colorless liquids whichwere separated by fractional distillation in vacuo (Tables II and III).

EXAMPLE 3 -- Addition of Trichlorosilane to 1,13-Tetradecadiene withUltraviolet Irradiation

A stirred mixture of 6.8 g (0.05 mole) trichlorosilane and 19.6 g (0.1mole) 1,13-tetradecadiene was irradiated in a closed quartz tube at 45°C for 72 hours with two Hanau 70 watt high pressure mercury immersionlamps, emitting a broad spectrum of ultraviolet light. The resultingcrude product was then fractionated to yield 5 g (25%) of13-tetradecenyl trichlorosilane as the monoadduct.

EXAMPLE 4 -- Reaction of 7-Octenyl Trichlorosilane with Methanol##STR15##

To 246 g (1 mole) stirred 7-octenyl trichlorosilane was added 48 g (1.5mole) methanol under N₂. The addition resulted in HCl evolution and someliquid phase separation. Subsequent heating at 65° C for 17 hoursresulted in a dark homogeneous liquid. This was fractionally distilledin vacuo to yield 119 g. colorless liquid 7-octenyldimethoxychlorosilane at 60-62° C. under 0.1 mm pressure. Analyses, Calcd. forC₁₀ H₂₁ ClO₂ Si: C, 50.72; H, 10.41. Found: C, 50.50; H, 9.52. The nmrspectrum shows the presence of two methoxy groups per terminal vinylicgroup, as expected for the assumed structure.

EXAMPLE 5. Reaction of 7-Octenyl Trichlorosilane with Sodium Methoxide

    Cl.sub.3 Si(CH.sub.2).sub.6 CH═CH.sub.2 + 3 NaOCH.sub.3 → (CH.sub.3 O).sub.3 Si(CH.sub.2).sub.6 CH═CH.sub.2 + 3 NaCl + O[Si(OCH.sub.3).sub.2 (CH.sub.2).sub.6 CH═CH.sub.2 ].sub.2

to a stirred 25% methanolic solution of 33.2 g (0.63 mole) sodiummethoxide, is added 50.2 g (0.21 mole) 7-octenyl trichlorosilane withcooling below 50° C. The crude product was filtered with suction toremove the sodium chloride and then fractionally distilled in vacuo. At48-49° C. under 0.1 mm pressure, 32 g (75%) of colorless liquid7-octenyl trimethoxysilane was obtained as the main product. At 127-128°C. under 0.1 mm, 6.5 g (15%) of slightly colored liquid bis-7-octenyldimethoxy disiloxane was received as a by-product.

Analyses, Calcd. for the trimethoxysilane, C₁₁ H₂₄ SiO₃ : C, 56.85; H,10.41. Found: C, 55.72; H, 9.53. Calcd. for the disiloxanes C₂₀ H₄₄ Si₂O₅ : C, 57.09; H, 10.54. Found: C, 56.04; H, 9.87. Both distillateproducts exhibited nmr spectra in accordance with their assumedstructures.

B. Synthesis of Silylalkyl Phosphines

EXAMPLE 6 -- Addition of Diphenyl Phosphine to Vinyl Trichlorosilane##STR16##

Into a quartz reaction vessel, equipped with a magnetic stirrer,nitrogen bubbler and a dropping funnel, was placed 13 g (0.07 mole) ofthe diphenyl phosphine reactant. To the stirred irradiated diphenylphosphine under nitrogen was added 11.3 g (0.07 mole) of vinyltrichlorosilane in 5 minutes. The irradiation of the stirred reactionmixture at 15° C., by 2 75-watt Hanau immersion lamps having a highpressure mercury arc emitting a wide spectrum of irradiation, wascontinued for 24 hours. A subsequent analysis by nuclear magneticresonance (nmr) spectroscopy of a sample indicated that an essentiallyquantitative addition reaction took place. No vinylic unsaturation waspresent in the final reaction mixture. The crude product was distilledin high vacuo to yield 19 g (80%) of distilled colorless liquid adductboiling at 142-144° C. at 0.1 mm.

For elemental analyses see Table IV.

EXAMPLE 7 -- Addition of Phenyl Phosphine to Vinyl Trichlorosilane##STR17##

In the manner described in the previous example, 22 g. (0.2 mole) ofphenyl phosphine was added to 64.6 g (0.4 mole) of vinyltrichlorosilane. Nmr spectroscopy of the crude adduct indicated theabsence of olefinic unsaturation. Fractional distillation in vacuoyielded 73 g (85%) of the clear, colorless liquid adduct boiling between131-132° C at 0.05 mm pressure.

EXAMPLE 8. Addition of Dihydrocarbyl Phosphines to ω-Alkenyl Silanes

In a manner described in Example 6, a number of secondary aromatic andaliphatic phosphines were added to the ω-alkenyl silanes described inExamples 1 to 5. The results of these addition experiments aresummarized in Table IV.

In general, equimolar reactants were used. However, it was found thatthe alkenyl silane conversion could be raised when twofold amounts ofthe phosphine reactant were used.

The addition of phosphines to allyl and higher alkenyl silanes isproceeding at rates slower than to those to vinyl silanes (Table IV,Ref. Nos. 1-3 vs. 4-9). Addition to allyl trichlorosilane seems to occurwith allylic reversal as a side reaction.

The addition of diphenyl phosphine to the olefinic unsaturation of thesilanes occurs more readily than that of the more basic dialkylphosphines (Table IV, Ref. Nos. 1, 7 vs. 2, 3, 8). The reduced reactionrate of the latter type of compounds is probably due to the increaseddonor interaction of their phosphorus atoms with the silicon.

These additions have a sharply reduced rate when internal alkenylsilanes are used in place of the ω-alkenyl compounds. The big ratedifference suggests that steric crowding is an important factor inlimiting the addition of bulky phosphinyl radicals to internal doublebonds.

The silylalkylphosphine adducts were, in general, colorless, highlyviscous liquids. Their high viscosity at room temperature is probably anindication of their high degree of molecular association due to P→ Siinteractions. They could be isolated by fractional distillation in highvacuo. Some of them were distilled at temperatures in excess of 200° C.without decomposition (Table IV, Ref. Nos. 5-10). This indicated thatthey possess a considerable thermal stability. The assumed structure ofthe adducts is supported by their elemental composition (Table IV). Thenon-branched polymethylene character of the alkylene groups bridging thephosphine and silane moieties is indicated by nmr.

                                      TABLE IV                                    __________________________________________________________________________    ω-SUBSTITUTED SILYLALKYL PHOSPHINES VIA PHOSPHINE ADDITION TO           ω-ALKENYL SILANES                                                        ##STR18##                                                                                          Yield,                                                                         %           Elemental Composition                      Ref.                  (After                                                                             Boiling Range                                                                         Calcd.      Found                          No.                                                                              Chemical Structure Hrs.*)                                                                              ° C./mm                                                                       C  H  P  Cl C   H   P   Cl                 __________________________________________________________________________    1  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.2 SiCl.sub.3                                             80(24)                                                                             142-144/0.1                                                                           48.37                                                                            3.98     48.19                                                                             3.98                       2  (C.sub.6 H.sub.11).sub.2 P(CH.sub.2).sub.2 SiCl.sub.3                                            33(72)                                                                             96-98/0.15                                                                            46.74                                                                            7.28  29.57                                                                            45.84                                                                             6.88    30.42              3  (C.sub.3 H.sub.7).sub.2 P(CH.sub.2).sub.2 SiCl.sub.3                                             50(24)                                                                             77-78/0.5                                                                             34.36                                                                            6.49                                                                             11.08 33.48                                                                             6.42                                                                              11.44                  4  (C.sub.6 H.sub.5).sub.2 P(CH.sub. 2).sub.3 SiCl.sub.3                                            38(96)                                                                             144-145/0.1                                                                           49.81                                                                            4.46                                                                             8.56                                                                             29.41                                                                            48.95                                                                             4.65                                                                              8.42                                                                              28.55              5  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3                                             70(37)                                                                             218-221/0.5                                                                           55.63                                                                            6.06                                                                             7.17                                                                             24.64                                                                            55.64                                                                             5.92                                                                              7.78                                                                              23.29              6  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 Si(CH.sub.3)Cl.sub.2                                   34(96)                                                                             188-189/0.1                                                                           61.31                                                                            7.10                                                                             7.53                                                                             17.24                                                                            60.45                                                                             6.60                                                                              7.84                                                                              16.30              7  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 Si)(OC.sub.2 H.sub.5).sub.3                            46(72)**                                                                           198-200/0.13                                                                          67.79                                                                            8.97     68.28                                                                             8.61                       8  (C.sub.6 H.sub.11).sub.2 P(CH.sub.2).sub.8 Si(OC.sub.3 H.sub.5).sub.3                            26(72)                                                                             195-197/0.1                                                                           66.06                                                                            11.30    66.04                                                                             10.50                      9  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.14 SiCl.sub.3                                            32(113)**                                                                          188-190/0.05                                                                          60.52                                                                            7.42                                                                             6.00  60.56                                                                             7.21                                                                              6.50                   10                                                                                ##STR19##         82(72)**                                                                           220-225/0.3                                                                           58.48                                                                            4.91                                                                             6.86                                                                             23.54                                                                            60.09                                                                             5.12                                                                              7.07                                                                              22.55              __________________________________________________________________________     *Irradiation by ultraviolet light.                                            **Two moles of phosphine per alkenyl silane were used.                   

EXAMPLE 9 -- Addition of Diphenyl Phosphine to 7-OctenylDimethoxychlorosilane

    (C.sub.6 H.sub.5).sub.2 PH + CH.sub.2 ═CH(CH.sub.2).sub.6 Si(OCH.sub.3).sub.2 Cl → (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 Si(OCH.sub.3).sub.2 Cl

A mixture of 40.7 g (0.2 mole) diphenyl phosphine and 23.24 g (0.1 mole)7-octenyl dimethoxy chlorosilane of Example 4 was irradiated at 15° for72 hours. An nmr spectrum of the resulting liquid product showed thedisappearance of most of the vinylic protons, indicating addition toform 8-dimethoxychlorosilyloctyl diphenyl phosphine. However, theproduct decomposed on attempted distillation in vacuo when heated to210° C.

C. Anchoring to Silica

EXAMPLE 10 -- Dehydration of Silica Used for Anchoring

Grade HSF cab-o-sil, having a surface area about 300 M² /g, obtainedfrom the Cabot Co., Boston, Mass., was heat-treated using a fluidizedsand bath equipped with high vacuum stopcock and O-ring construction for16 hours at >325° C. at 10⁻⁴ mm Hg vacuum pressure. According to theliterature (see Advances in Catalysis and Related Subjects, Vol. 16, Ed.D. D. Eley, H. Pines, and P. B. Weise, H. P. Boehm, particularly pages242-244, Acad. Press., New York, 1966), the above heat treatment ofsilica is sufficient to remove physically absorbed water. According tothe above-referred literature the heat treated cab-o-sil so obtained hasabout 3 silanol groups per 10⁻⁶ cm² silica surface. One g cab-o-sil has3 × 10⁶ cm² surface which means 1.5 × 10⁻³ mole equivalents of silanol.The above treated cab-o-sil was then transferred to a dry box and storedin a tightly capped bottle until use.

EXAMPLE 11 -- Reaction of the Phosphine (C₆ H₁₁)₂ P(CH₂)₂ SiCl₃ withDehydrated Cab-o-sil

A 1.87 g portion of (C₆ H₁₁)₂ P(CH₂)₂ SiCl₃ (5.0 mm) was dissolved in 40ml benzene and added to 12.5 g dehydrated cab-o-sil of Example 10 in 5ml portions with thorough grinding. The benzene was removed from thecab-o-sil by vacuum drying at 5 × 10⁻² mm Hg vacuum pressure for threehours at room temperature. The impregnated cab-o-sil was then heated at100° C. at 5 × 10⁻² mm Hg pressure for sixteen hours. A sample of thephosphine on cab-o-sil was submitted for C, H, P, Cl analysis. Found: C,6.85; H, 1.16; P, 1.10; Cl, 1.51. Calculated (assuming the phosphine (C₆H₁₁)₂ P(CH₂)₂ SiCl₃ was unreacted on the cab-o-sil surface): C, 6.07; H,0.95; P, 1.12; Cl, 3.84. All operations involving air sensitivematerials were performed in a nitrogen purged dry box. This exampledemonstrates that the above heat-treatment of this phosphine, ondehydrated cab-o-sil will eliminate 1.81 moles hydrogen chloride permole phosphine from the cab-o-sil surface.

EXAMPLE 12 -- Reaction of The Anchored Phosphine of Example 11 WithRhodium Carbonyl Chloride

A 5.76 g portion of the anchored phosphine, Example 11 containing 2.0 mmof phosphine, was impregnated with the light yellow solution of 0.194 g.[(CO)₂ RhCl]₂ (0.50 mm) dissolved in 15 ml benzene. The impregnatedcomplex was ground for 20 minutes to insure a homogeneous distributionof rhodium carbonyl chloride on the cab-o-sil surface. Followingthorough mixing, the impregnated cab-o-sil was dried at ambienttemperature for 1 hour at 5 × 10⁻² mm Hg vacuum pressure. Sixty ml ofbenzene was then added and the mixture was stirred for 10 minutes. Themixture was then suction filtered through a fine glass filter frit.Complete retention of the rhodium complex [(C₆ H₁₁)₂ P(CH₂)₂ SiCl₃ ]₂Rh(CO)Cl, on the cab-o-sil surface, was evidenced by the water whitecolor of the benzene filtrate. The impregnated rhodium complex was thendried for 16 hours at 10⁻² mm Hg vacuum pressure at 50° C. A sample ofthe anchored rhodium complex was submitted for C, H, Rh, P, Cl analyses.Found: C, 6.84; H, 1.26; Rh, 1.86; P, 1.06; Cl, 1.42; Calculated(assuming the complex [(C₆ H₁₁)₂ P(CH₂)₂ SiCl₃ ]₂ Rh(CO)Cl was theproduct of the above reaction); C, 6.36; H, 0.96; Rh, 1,88; P, 1.13; Cl,4.53.

This example demonstrates the ready formation of an anchoredphosphine-rhodium complex by impregnation of rhodium dicarbonyl chloridedimer onto phosphine anchored to cab-o-sil below its point of incipientwetness.

EXAMPLE 13 -- Anchoring of Various Silylalkyl Phosphines and TheirTransition Metal Complexes

In a series of experiments the dehydrated silica of Example 10 wasreacted with about 0.2×10⁻³ mole of a trichlorosilylalkyl phosphine orits transition metal complex per g silica. In general, the novelanchored complexes were prepared in benzene, which is a good solvent forboth the free and complexed phosphines.

In most cases, the complexing of silyalkyl phosphines was effected afteranchoring to silica. The occurrence of complexing was then establishedby analyzing the modified silica for metal as well as phosphoruscontent. As indicated by the data of Table V, the found and calculatedphosphorus contents are in good agreement. In general, the transitionmetal compound reactants were employed in stoichiometric amounts inbenzene solutions. Quantitative reaction with the anchored phosphinecomplexes was indicated by the absence of the color of the metal complexfrom the benzene after treatment. The structure of all the complexescontaining a carbonyl group remained unchanged; as indicated by a singlestrong carbonly stretching frequency in the 1960-1990 cm⁻¹ region of theinfrared spectra of the complexes follow exposure to a carbon monoxideatmosphere.

Typical methods of anchored silylalkyl phosphine-rhodium complexpreparation, referred to in Table V, are outlined below:

A. About 4% benzene solution of 2m mole silylalkyl phosphine-rhodiumcomplex was added to 10 g dehydrated cab-o-sil with thorough grinding toeffect impregnation. Benzene was then removed at a pressure of 0.05mmand hydrogen chloride eliminated by heating at 140° C. for 14 hours.

On about 5.7 g sample of modified methanol treated cab-o-sil having 2mmole of anchored silylalkyl phosphine was impregnated with a 20 mlbenzene solution of 0.5m mole of rhodium compound. The benzene was thenremoved in vacuo and the dried product washed with 60 ml benzene,filtered, with suction and dried at 50° C. for 3 hours at 0.05 mmpressure.

C. A procedure similar to B was followed starting with cab-o-sil notsubsequently exposed to methanol.

D. A procedure similar to B was followed, but the washing with benzeneomitted.

E. A procedure similar to A was followed plus the product was treatedwith excess methanol at ambient temperature.

In general, at least one mole of hydrochloric acid per mole phosphinewas eliminated presumably by the following anchoring reaction: ##STR20##The degree of this type of reaction was reflected in the chlorinecontent of the anchored phosphine (Tables V and VI). The phosphoruscontent was generally about 1%.

    Table V      Preparation of Rhodium Complexes of n-(Trichlorosilyl)-alkyl Phosphines     Anchored to Silica Via the Reaction      ##STR21##      Form of  Rhodium Compound - Anchored Phosphine Complex Method Phosphine     Rhodium Disregarding HCl Elimination on Anchoring to Silica of Seq     Anchoring Compound Calculated Compositon, % Prepara- Found Composition,     % No. Reagent Reagent Chemical Structure C H Rh P Cl tion C H Me P     Cl      1 Complex Rh(CO).sub.2 Cl.sub.2 [(C.sub.6 H.sub.5).sub.2     P(CH.sub.2).sub.2 SiCl.sub.3 ].sub.2 Rh(CO)Cl 5.99 0.48 1.77 1.07 4.27 A 6     .44 0.88 1.53 0.90 2.53 2 Free        B(CH.sub.3 OH) 7.25 0.93 1.65 1.12     1.48 3 Free  [(C.sub.6 H.sub.11).sub.2 P(CH.sub.2).sub.2 SiCl.sub.3     ].sub.2 Rh(CO)Cl 6.36 0.96 1.88 1.13 4.53 C 6.84 1.26 1.86 1.06 1.42 4     Free  [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3 ].sub.2     Rh(CO)Cl 8.17 0.87 1.71 1.03 4.11 D(CH.sub.3 OH) 9.18 1.16 1.70 1.02     0.70 5 Free [Rh(1,5-COD)Cl].sub.2 [(C.sub.6 H.sub.5).sub.2      P(CH.sub.2).sub.2 SiCl.sub.3 ].sub.3 RhCl 5.77 0.48 1.18 1.06 4.06 B     7.88 1.01 1.77 1.08 1.08 6 Free  [(C.sub.6 H.sub.11).sub.2      P(CH.sub.2).sub.2 SiCl.sub.3 ].sub.3 RhCl 6.36 0.98 1.29 1.16 4.44 C     7.36 1.52 1.16 1.03 2.02 7 Free  [(C.sub.6 H.sub.5).sub.2      P(CH.sub.2).sub.8 SiCl.sub.3 ].sub.3 RhCl 8.04 0.88 1.15 1.07 3.96 B     9.07 1.18 1.28 1.09 0.60 8 Complex  (C.sub.6 H.sub.5).sub.2      P(CH.sub.2).sub.2 SiCl.sub.3 Rh(1,5-COD)Cl 8.54 0.85    E(CH.sub.3 OH)     6.03 0.74 9 Complex  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.2      Si(OC.sub.2 H.sub.5).sub.3 Rh(1,5-COD)Cl 9.86 1.22    A 5.24 0.76 10     Complex  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3      Rh(1,5-COD)Cl 10.6 1.20 3.23 0.97 4.45 A 10.31  1.34 3.44 1.15 3.57 11     Complex  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.14 SiCl.sub.3      Rh(1,5-COD)Cl 12.51 1.54    E(CH.sub.3      OH) 7.48 1.35

    Table VI      Preparation of Palladium and Cobalt Complexes of 8-(Trichlorosilyl)-octy     l Phosphine and 2-(Trichlorosilyl)-ethyl Diphenyl Phosphine Anchored to     Silica  Transition Metal-Anchored Phosphine Complex Method Transition         Disregarding HCl Elimination on Anchoring to Silica of Seq. Compound C     alculated Composition, % Prepara- Found Composition, % No. Reagent     Chemical Structure C H Me P Cl tion C H M P Cl       1 Pd(AcAc).sub.2 * (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8      SiCl.sub.3 Pd(AcAc).sub.2 11.31 1.26 3.34 0.97 3.34 B(CH.sub.3 OH)     10.37 1.34 2.35 1.02 1.51 2 (C.sub.6 H.sub.5 CN).sub.2 PdCl.sub.2     [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3 ].sub.2 PdCl.sub.2     7.95 0.87 1.76 1.02 4.69 A 8.47 0.72 1.73 1.08 1.84 3  (C.sub.6      H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3 Pd(C.sub.6 H.sub.5      CN)Cl.sub.2 5.68 0.55 1.86 0.54 3.10 A 7.43 1.05 1.73 0.86 2.39 4     Co(CO).sub.8 [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.2 SiCl.sub.3     ].sub.2      Co(CO).sub.6   5.97 3.08 10.8 A**   6.85 2.18 11.1 5 Co(CH.sub.3)(CO).su     b.4 (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.2 SiCl.sub.3 Co(CO)CH.sub.3     (CO).sub.3 4.14 0.31 1.07 0.56 1.92 A 3.42 0.62 0.84 0.38 2.30     *Palladium bisacetyl acetonate.     **The complex (4.9 g, 5m mole) was dissolved in a minimum volume of     benzene, and the solution added to 5g cab-o-sil with thorough mixing. The     mixture was then evacuated and heated at 140° C. for 2 hours at     0.05mm to remove the solvent and the hydrogen chloride formed.

                                      Table VII                                   __________________________________________________________________________    Anchoring Reactions of 2-(Trichlorosilyl)-ethyl Diphenyl Phosphine with       Silica                                                                        and Subsequent Reactions with Methanol of the Resulting Anchored              Phosphine                                                                      ##STR22##                                                                    Phosphine,                                                                              Reaction Conditions (Sequential)                                                                  After Treatment                                                                        Found Composition, %                   Seq.                                                                             m mole in Benzene                                                                             After Drying                                                                             Soxlet Extraction                                                                      (Calcd. for Reactant Mixture)          No.                                                                              per g silica                                                                         ° C.                                                                       hrs. ° C.                                                                      hrs.                                                                              mm  Solvent (Reagent)                                                                      C     H     P     Cl                   __________________________________________________________________________    1  1.6                                 (17.58)                                                                             (1.48)                                                                              (3.24)                                                                              (11.12)                 (dehydrated)                                                                         25  <3   155                                                                              18  0.05         20.16 1.77  3.60  7.49                                               Dry Benzene                                                                            12.92 1.40  2.16  3.82                                               Wet Benzene                                                                            13.03 1.30  1.92  1.69                                               Methanol, then                                                                         13.55 1.35  1.92  0.97                                               Pyridine/Benzene                                2  6                                   (32.69)                                                                             (2.74)                                                                              (6.02)                                                                              (20.6)                  (hydrated)                                                                           80  4     25                                                                               2  0.05         13.35 1.35  2.21  2.39                                               Dry Benzene                                                                            12.27 1.17  2.22  1.66                 3  0.4                                 (5.90)                                                                              (0.50)                                                                              (1.09)                                                                              (3.73)                  (dehydrated)                                                                         25  2                        7.19  0.87  1.15  2.18                                               Methanol 7.12  0.83  1.14  1.03                 __________________________________________________________________________

EXAMPLE 14 -- Stability of Anchored Trichlorosilylated Phosphines

The anchoring of 2-(trichlorosilyl)-ethyl diphenyl phosphine and thestability and reactivity of the resulting anchored phosphine was studiedin some detail. The results are summarized in Table VII. The data showthat using an excess of the phosphine, about 1m mole phosphine can beanchored to 1g silica, i.e., to a surface of 3 × 10⁶ cm². Anchoring,involving one chlorine of the silyl group, occurs even at roomtemperature to either the dehydrated or hydrated silica. The anchoredphosphine is stable to extraction by either benzene or methanol.However, methanol or water does react with the chlorosilyl groups asindicated by the decreased chlorine contents. About one chlorine perphosphorus atom still remained in the anchored composition. It is felt,however, that this chlorine may have migrated from the original siliconatom it was attached via reversible chlorosilane hydrolysis. Anyhydrogen chloride formed will also complex reversibly with the phosphinegroups.

As a result of water or methanol treatment, some of the chlorosilanegroups are converted to silanol groups. These in turn might undergosiloxane condensation.

    2 Si--Cl .sup.+ H.sbsp.2.sup.O  2 Si--OH .sup. -H.sbsp.2.sup.O  Si--O--Si

EXAMPLE 15 -- Anchoring a Phosphine at Room Temperature and itsSubsequent Reaction with Methanol

A 4.33 g portion of φ₂ P(CH₂)₈ SiCl₃ (10.0 mm) was impregnated onto 25 gdehydrated cab-o-sil utilized two impregnations of 4 mm of φ₂ P(CH₂)₈SiCl₃ dissolved in 40 ml benzene onto two-10 g portions of dehydratedcab-o-sil, and one impregnation of 2 mm of φ₂ P(CH₂)₈ SiCl₃ dissolved in20 ml benzene onto one 5 g portion of dehydrated cab-o-sil. The threeportions were combined in a 1000 cc side arm vacuum flask and dried forthree hours at ambient temperature at 5 × 10⁻² mm Hg vacuum pressure. A300 ml portion of methanol was added to the impregnated phosphine andthe mixture was refluxed with stirring for 2 hours. The mixture was thenvacuum filtered through a fine glass filter frit and the residue waswashed with two 50 ml portions methanol. The residue was dried for 16hours at 80° C. at 5 × 10⁻² mm Hg vacuum pressure. A portion of themethanol washed sample was submitted for C,H, P, Cl analysis: Found: C,9.12; H, 1.18; P, 1.04; Cl, 0.21; Calculated (assuming the phosphineφP(CH₂)₈ SiCl₃ was unreacted on the cab-o-sil surface) C, 8.19; H, 0.89;P, 1.06; Cl, 3.63. This example again demonstrates the reaction of atrichlorosilylated phosphine with dehydrated cab-o-sil at ambienttemperature. This example also demonstrates that the chlorosilyl groupshave increased reactivity towards methanol if they are separated fromthe phosphine group by a polymethylene chain.

D. Catalysis Using Anchoring Phosphine - Metal Complexes

EXAMPLE 16 -- Anchored Catalysts of Propylene Hydroformylation andCyclohexene Hydrogenation

Propylene hydroformylation catalytic activity of the heterogeneousrhodium catalysts of Example 13, Table V, Sequence Nos. 3, 6, 2, 5, 4,7, 10, 8, 11, 9 were impregnated in an Autoclave Engineer's 300 cccapacity autoclave. The heterogeneous rhodium catalysts were placed in aglass liner to which 70 ml benzene had been added. All operations wereperformed in a nitrogen purged dry box. The glass liner was sealed witha rubber stopper and transferred to the autoclave where the glass linerwas blanked by a purge of argon during assemblage of the autoclavestirrer. Propylene was introduced to the stirred benzene solution untilthe benzene solution was saturated. The propylene concentration wasfound to be reasonably constant by the above procedure. The temperaturewas increased to 100° C. and CO/H₂ (50:50 blend) was added to give atotal pressure of 1000 psi. The temperature was increased slowly up to amaximum temperature of 180° C. The total CO/H₂ absorbed was noted aswell as the time and temperature at each increment.

Propylene was hydroformylated to form mainly butyraldehyde in asaturated benzene solution. The activity of the various catalystsstudied was observed at the 0.1-0.5m mole level as a function of CO/H₂absorbed. During the experiment the temperature of the mixture wasincreased to either a maximum of 180° C. or to the temperature ofvirtually complete conversion. While the reaction was in progress, thepressure drop from 1000 psi was recorded and the pressure readjustedrepeatedly. The relative rate of the reaction was semi-quantitativelydetermined by summing up the pressure drop during the period ofobservation. The greater the pressure drop and the lower the temperatureand the shorter the reaction time are, the higher the reaction rate iswith a certain catalyst.

In the cyclohexene hydrogenation studies, a 1M benzene solution was usedwith a catalyst containing 2.5m mole rhodium. At a constant, 50 psigpressure of hydrogen, the temperature necessary to reach a 1 psig perminute hydrogen uptake was determined for each catalyst.

The results of both hydroformylation and hydrogenation studies are shownby Table VIII. They indicate that several of the anchored catalysts haveactivities comparable to homogeneous catalysts of similar structure.Most interestingly the results also show that the activities aredependent on the length of the alkylene chain linking the phosphineligand to the silica. Furthermore, the effect of the alkylene chain onthe catalytic activity is dependent on the method of ahchoring and onthe reaction being examined. Both the kind of reactive anchoring groupsand the length of the alkylene group have a profound effect onhydroformylation but no significant effect on hydrogenation activity.

In the hydroformylation reaction, the catalysts derived by complexinganchored 2-(trichlorosilyl)-ethyl phosphines, i.e., trichlorosilylphosphines having a two carbon alkylene chain (Sequence Nos, 1, 2, 5, 7,9), are completely inactive. In contrast, analogous2-(triethoxysilyl)-ethyl phosphine derived catalysts (Sequence Nos. 6,10) are very active. Also in contrast, the use ofanchored-(trichlorosilyl)-alkyl phosphines having longer alkylenechains, i.e., octamethylene or tetradecamethylene groups (Sequence Nos.3, 4, 8, 11, 12) led to very active rhodium catalysts.

A comparison of the hydroformylation catalysts derived from8-(trichlorosilyl)-octyl diphenyl phosphine (Ref. Nos. 3, 6, 8, 11)indicate that the degree of activity is directly proportional with thephosphine coordination number at the metal center. For example, the L Rh(1,5-COD)Cl complex (No. 11) is much more active than the L₃ RhClcomplex (No. 8).

In the hydrogenation reaction, the structure of the anchoring reagenthas little, if any, effect. With the exception of the anchored complexeshaving a carbonyl ligand (Ref. Nos. 1-3), all the compositions wereactive. In contrast to the hydroformylation, hydrogenation rates wereincreased with increasing phosphine coordination number at the metalcenter. For example, the L Rh(1,5-COD)Cl complexes (Nos. 9 and 11) areless active hydrogenation catalysts than the corresponding L₃ RhClcomplexes (Nos. 5 and 8).

It was interesting to compare the catalytic activity of anchored complexcatalysts and soluble complex catalysts of similar structure. It wasfound that the activity of the best anchored caatalysts forhydroformylation (Nos. 10-12) and hydrogenation (Nos. 5 and 8) is of thesame order of magnitude as that of the soluble triphenylphosphinerhodium chloride (No. 13). However, it has to be pointed out that adirect comparison of activities is most difficult. The soluble catalystcomplex (No. 13) has no activity whatsoever in the presence ofcab-o-sil. The hydroxyl groups of silica apparently completely inhibitits catalytic activity.

    Table VIII        Hydrogenation  Hydroformulation  Temperature Seq. Rhodium Reactants     Reaction Conditions Activity Estimate Cat. 1 psig C-173 Seq. Rhodium     Compound-Anchored Phosphine Complex No. in Catalyst (CO/H.sub.2)     Consumed, Temperature Time Hydro- Hydrogena- per min. H.sub.2 Ref. No.     Disregarding HCl Elimination on Anchoring Ex. 13 m mole psi drop Range,     °      C Min. formulation tion uptake No.                                1     [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.2 SiCl.sub.3 ].sub.2 Rh(CO)Cl 1 0     .5 0 100-160  72 None None -- -- 2 [(C.sub.6 H.sub.11).sub.2      P(CH.sub.2).sub.2 SiCl.sub.3 ].sub.2 Rh(CO)Cl 3 0.5 0 100-180  77 None     -- -- -- 3 [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3 ].sub.2     Rh(CO)Cl 4 0.1  115 100-175 118 Moderate None -- -- 4 { [(C.sub.6     H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3 ].sub.2 RhCl}.sub.2 -- -- --     -- -- -- Moderate 95 -- 5 [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.2     SiCl.sub.3 ].sub.3 RhCl 5 0.4 0 100-155  83 None High 70 63 6 [(C.sub.6     H.sub.5).sub.2 P(CH.sub.2).sub.2 Si(OC.sub.2 H.sub.5).sub.3 ].sub.3 RhCl      0.5 1100 100-175 134 Moderate -- -- -- 7 [(C.sub.6 H.sub.11).sub.2     P(CH.sub.2).sub.2 SiCl.sub.3 ].sub.3 RhCl 6 0.3 0 100-165 143 None -- --     -- 8 [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3 ].sub.3 RhCl     7 0.1  195 100-145 151 Moderate High 70 59 9 (C.sub.6 H.sub.5).sub.2     P(CH.sub.2).sub.2 SiCl.sub.3 Rh(1,5-COD)Cl 8 0.5 0 100-175  75 None     Moderate 80 65 10  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub. 2      Si(OC.sub.2 H.sub.5).sub.3 Ph(1,5-COD)Cl 9 0.5 1070 100-150 149 High --     -- -- 11  (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3      Rh(1,5-COD)Cl 10  0.5 1160 100-140 176 High Moderate 90 58 12  (C.sub.6     H.sub.5).sub.2 P(CH.sub.2).sub.14 SiCl.sub.3 Rh(1,5-COD)Cl 11  0.5 1160     100-150 154 High -- -- -- 13  [(C.sub.6 H.sub.5).sub.3 P].sub.3 RhCl 4 1      780 150  25 High High 55 66 14  [(Rh(1,5-COD)Cl].sub.2 -- -- -- -- --     -- High 75 70

Hydrogenation of cyclohexene was investigated for a number of anchoredrhodium phosphine complexes of the formula L_(x) RhCl, where x = 1, 2, 3and where L is a trichlorosilylated phosphine chemically affixed tocab-o-sil, in order to establish the sensitivity of the hydrogenationreaction rate to coordination number about the metal and to the type ofphosphine. The active homogeneous hydrogenation catalyst (φ₃ P)₃ RhClwas used as comparison to the anchored rhodium phosphine catalystsinvestigated. Standard cyclohexene hydrogenation conditions weredetermined by investigating the activity of 0.125 mm (φ₃ P)₃ RhClcatalyst in 50 ml of 1M solution of cyclohexene (dried over sodium metaland stored under nitrogen in benzene. The catalyst concentration was 2.5mM in rhodium catalyst. All hydrogenation reactions were investigated ata constant hydrogen pressure of 50 psig. The temperature of hydrogenuptake of about 1 psig per minute was determined for each catalyst. Allof the hydrogenation reactions were investigated using a 300 cc capacityFisher high pressure reaction bottle equipped with pressure gauge andgas inlet and outlet valves.

EXAMPLE 17 -- Activity Maintenance of Anchored rhodium phosphine complexin Propylene Hydroformylation

Because of the marked greater activity of catalyst No. 11 of Table VIIIa number of recycling steps with the catalyst were performed anddemonstrated an increase in catalytic activity with no apparent decreasebeyond a consistently high activity. A 0.5 mm, as rhodium gave a totalof 420 pounds CO/H₂ uptake over a 210 minute interval with a finaltemperature of 175° C. The catalyst from the above hydroformylation runwas suction filtered through a fine sintered glass frit. The residue waswashed with 100 ml benzene. Before the rhodium complex on cab-o-sil wasallowed to dry, the catalyst was recharged for another hydroformylationrun. The catalyst was carried out over a time interval of 86 minutes at135° C. with a total CO/H₂ consumption of 1320 pounds. The catalyst wasfiltered, washed with 100 ml benzene and recharged as previouslydescribed above. The catalysis was carried out over a time interval of175 min. at 135° C. with a total CO/H₂ comsumption of 1160 pounds.Normal butyraldehyde to iso-butyraldehyde ratio was 1.05 and 1.25 forthe latter two runs, respectively. Similar effectiveness is observed foran analogous homogeneous triphenylphosphine complex catalyst. Thisexample demonstrates that the anchored rhodium-phosphine catalysts areeffective for hydroformylation and retain their activity through severalcycles.

EXAMPLE 18 -- Maintenance of Cyclohexene Hydrogenation activity of theanchored rhodium phosphine complex where Rh: P ratio is 1:1.

The catalyst benzene mixture was clear and light yellow in color. Areaction rate of 1 psig H₂ /min. was observed at 115° C. The reactionmixture was taken into a nitrogen purged dry box and suction filteredwith a fine sintered glass filter frit. The residue was washed with 100ml benzene and rechanged for another hydrogenation run. The reactionsolution was clear and light grey in color. The hydrogenation rate ofthe recycled catalyst was the same as the initial hydrogenation rate.The reaction mixture was taken into a nitrogen purged dry box andsuction filtered through a fine sintered glass filter frit. The residuewas washed with 100 ml benzene and recharged for another hydrogenationrun following exposure of the reaction mixture to 50 psi carbon monoxidefor fifteen minutes with vigorous stirring. The carbon monoxide wasvented and the reactor was pressured with 50 psig H₂. The exposure ofthe hydrogenation catalyst to carbon monoxide completely inhibitedcatalytic hydrogenation activity of cyclohexene up to a temperature of157° C.

This example demonstrates that the anchored rhodium phosphine complexwith Rh:P ratio of 1:1 can be repeatedly recycled without decrease incatalytic dehydrogenation activity. This example also demonstrates thepoisoning effect of carbon monoxide on the catalytic hydrogenationactivity of the anchored rhodium catalyst. Carbon monoxide poisoning wasalso observed for rhodium black and (φ₃ P)₃ RhCl. This example providesa comparison between the catalytic hydrogenation activity of the aboveanchored catalyst with a Rh:P ratio of 1:1 and the anchored catalystwith a Rh:P ratio of 1:3. The catalytic hydrogenation activity isgreater for the latter catalyst. This example also provides a comparisonbetween the catalytic hydrogenation activity of anchored rhodiumcatalysts prepared by different techniques. The in situ preparation ofthe anchored rhodium catalyst with a Rh:P ratio of 1:1 is significantlymore active.

EXAMPLE 19 -- Hydrogenation of cyclohexene using 1,5-cyclo-octadienerhodium chloride dimer in the presence of dehydrated cab-o-sil.

The homogeneous hydrogenation catalyst 1,5-cyclo-octadiene rhodiumchloride dimer exhibited a reaction rate of 0.365 psig H₂ /min. at 100°C. The mixture was a grey color at this temperature. The reaction wasstopped after a total hydrogen consumption of 13 psig. The hydrogen wasvented from the reactor and the reactor was pressured to 50 psig withcarbon monoxide for 15 minutes with vigorous stirring of the reactionsolution. The carbon monoxide was vented from the reactor and thereactor was pressured with 50 psig H₂. The homogen ous catalyst wasinactive for cyclohexene hydrogenation up to a temperature of 100° C.

This example is provided only as a comparison to the anchored catalystsof the previous examples. This example demonstrates the significantreduction of the hydrogenation activity of 1,5-cyclooctadiene rhodiumchloride dimer by dehydrated cab-o-sil. It also demonstrates thepoisoning effect of carbon monoxide on the 1,5-cyclooctadiene rhodiumchloride complex in the presence of cab-o-sil.

EXAMPLE 20 -- Methanol Carbonylation Using An Anchored Phosphine-RhodiumComplex (a) Preparation of [(φ₂ P(CH₂)₂ SiCl₃ ]₂ Rh(CO)Cl

Dichlorotetracarbonyl dirhhodium, 2.80 g (7.2 mm), was dissolved in 50ml of benzene. A 10 g portion of φ₂ P(CH₂)₂ SiCl₃ (28.8 mm), dissolvedin 50 ml benzene was added slowly with stirring to thedichlorotetracarbonyl dirhodium. Reaction was evidenced by the immediatecolor change on mixing the two solutions from orange to light yellowwith rapid gas evolution from solution. After ten minutes of vigorousstirring, benzene was removed by vacuum drying (5 × 10⁻² mm Hg). Theresidue, following vacuum drying, was washed with four-5 ml portionhexane to yield 12.40 grams of the expected yellow crystalline product,[φ₂ P(CH₂)₂ SiCl₃ ]₂ Rh(CO)Cl, in essentially 100° % yield. The yellowcrystalline product had a melting point 168-169° C., decomposing onmelting to a deep red liquid. The complex [φ₂ P(CH₂)₂ SiCl₃ ]₂ Rh(CO)Clexhibited a single strong carbonyl stretching frequency at 1977 cm⁻ 1compared to the (φ₃ P)₂ Rh(CO)Cl carbonyl stretching frequency inbenzene of 1975 cm⁻¹. The crystalline complex was submitted for C, H,Rh, P, Cl analysis, Found: C, 40.63; H, 3.25; Rh, 12.2; P, 6.94; Cl,28.13; Calculated C29H280, RhSi2Cl2p2: C, 40.42; H, 3.28; Rh, 11.94; P,7.19; Cl, 28.8.

This example demonstrates the ability to prepare and isolate an L₂Rh(CO)Cl complex where L is a trichlorosilyl group containing phosphine.

(b) Reaction of [φ₂ P(CH₂)₂ SiCl₃ ]₂ Rh(CO)Cl with dehydrated cab-o-sil

A 1.72 g portion of [φ₂ P(CH₂)₂ SiCl₃ ] Rh(CO)Cl (2.0 mm was dissolvedin 40 cc benzene. The benzene solution was added dropwise to 10 gdehydrated cab-o-sil with thorough grinding. Benzene was removed fromthe rhodium complex impregnated onto cab-o-sil by vacuum drying atambient temperature for 1 hr. at 5 × 10⁻² mm Hg vacuum pressure. Therhodium complex impregnated onto cab-o-sil was then heated at 140° C.for 14 hours at 5 × 10⁻² mm Hg vacuum pressure. The above heat treatmenteliminated hydrogen chloride gas from reaction of the chlorosilanegroups with the hydroxyl groups of the silica surface as analysis of theliquid nitrogen vacuum trap from the fourteen hour heat treatment gaveacid concentration equivalent to 0.25 mm HCl per mm rhodium. Directchemical analysis of the rhodium complex on cab-o-sil indicated 2.8 mmchlorine per mm rhodium had been removed from the cab-o-sil surface ashydrogen chloride, as shown by the following. Found: C, 6.44; H, 0.88;Rh, 1.53; P, 0.90; Cl, 2.53; calculated (determined on the assumptionthat the complex [φ₂ P(CH₂)₂ SiCl₃ ]₂ Rh(CO)Cl was present on thecab-o-sil surface according to the concentration above, i.e., 2 mmrhodium complex/10 g cab-o-sil: C, 5.93; H, 0.48; Rh, 1.73; P, 1.06; Cl,4.23.

The above example demonstrates again the facile reaction of atrichlorosilylated phosphine-rhodium complex with dehydrated cab-o-sil.

(c) The anchored phosphine rhodium complex as a methanol carbonylationcatalyst

A 2.95 g portion of [φ₂ P(CH₂)₂ SiCl₃ ]₂ Rh(CO)Cl/cab-o-sil (0.5 mm asrhodium), was placed in a glass liner of a 200 cc capacity Rothautoclave with 63 ml methanol and 7 ml benzene. Methyl iodide was usedas a co-catalyst and 0.25 ml was added to the above mixture. The 200 cccapacity Roth autoclave was sealed in the dry box and transferred to thehood. Magnetic stirring was used during the course of the reaction. TheRoth autoclave was then pressurized with CO at ambient temperature to250 psi. The temperature was increased to 145° C. and maintained for 17hours. Quantitative g.c. analysis of the distilled reaction solutiongave the following wt. percent of components; H₂ O, 5.0; CH₃ OH, 75.7;CH₃ CO(OCH₃), 10.5; C₆ H₆, 8.8. Analysis of a portion of severalcatalysts following analogous methanol carbonylation run conditionsusing the above conditions and the same rhodium complex, demonstratethat the rhodium complex had remained affixed to the cab-o-sil surfaceunder reaction conditions. Analysis of several spent methanolcarbonylation runs with the above anchored catalyst is given toillustrate the ability of the anchored rhodium complex to function as aheterogeneous catalyst in slurry reactions without loss of the preciousmetal: Found: Spent catalyst from run #A: C, 6.28; H, 0.89; Rh, 1.59; P,0.75: Cl, 0.63; spent catalyst run #C; C, 6.76; H, 0.84, Rh, 1.63; P,0.95; Cl, 1.23 spent catalyst run #G; C, 6.63, H, 1.14, Rh, 2.02; P,0.91; Cl, 1.15. The above elemental compositions compare well with thatof the starting anchored catalyst except for the decreased chlorinevalues.

This example when compared with the following experiment demonstratesthe near equivalent methanol carbonylation activity of the anchoredrhodium complex compared to the analogous homogeneous catalyst (φ₃ P)₂Rh(CO)Cl. This example also demonstrates the retention of the rhodiummetal on the cab-o-sil surface under methanol carbonylation reactionconditions.

(d) (φ₃ P)₂ Rh(CO)Cl as a methanol carbonylation catalyst.

A 0.345 g amount of (φ₃ P)₂ Rh(CO)Cl was placed in a glass liner for a200 cc capacity Roth autoclave with 63 ml methanol/7 ml. benzene. Methyliodide was used as a co-catalyst and 0.125 ml was added to the abovemixture. The 200 cc capacity Roth autoclave was sealed in the dry boxand transferred to the hood. Magnetic stirring was used during thecourse of the reaction. The autoclave was then pressurized with CO atambient temperature to 250 psi. The temperature was increased to 175° C.and maintained for 20 hrs. Quantitative g.c. analysis of the distilledreaction solution gave the following weight percent of components: H₂ O,11.2; CH₃ OH, 63.3; (CH₃)₂ O, 3.8; CH₃ CO(OCH₃), 11.1; CH₃ COOH, 0.1; C₆H₆, 10.5.

This example is included only to provide a comparison of the activity ofa homogeneous methanol carbonylation catalyst to the heterogeneousmethanol carbonylation catalyst.

(e) Blank runs of the methanol carbonylation reactor

(1) A 2.5 g amount of dehydrated cab-o-sil, was placed in a glass linerof a 200 cc capacity Roth autoclave with 45 ml methanol/7 ml benzenesolution. Methyl iodide (0.5 ml) was added and the Roth autoclave wassealed in the dry box and transferred to the hood. The autoclave waspressured at ambient temperature to 250 psi CO at ambient temperature.Magnetic stirring was used during the course of the reaction. Gaschromatographic analysis showed no methyl acetate was produced for a runtime of sixteen hours at 140° C. (2) A 0.25 ml portion of methyl iodidewas placed in a 200 cc capacity Roth autoclave with 63 ml methanol/7 mlbenzene. The Roth autoclave was sealed in the dry box and transferred tothe hood. The autoclave was pressured to 250 psi CO at ambienttemperature. The temperature was increased to 150° C. and maintained forsixteen hours. Quantitative g.c. analysis gave the following weightpercent; H₂ O, 6.1; (CH₃)₂ O, 6.0; CH₃ OH, 75.5; CH₃ CO(OCH₃), 0.1; C₆H₆, 11.3.

This example is included only to provide a demonstration that cab-o-siland methyl iodide, or methyl iodide in the absence of cab-o-sil are notcatalytic for methanol carbonylation under the reaction conditionsemployed in (c) and (d) above.

(f) The anchored phosphine of (b) exposed to benzene Soxlet extractionand concentrated acetic acid at 150° C

To establish that the anchored phosphine rhodium complex of (c) wouldremain intact as a heterogeneous phase in the presence of various liquidphases, the following experiments were executed: (1) A portion of theanchored phosphine rhodium complex of (c) was heated for two hours at150° C. in 100 ml concentrated acetic acid in a 200 cc capacity Rothautoclave. The above acetic acid solution was suction filtered through afine glass filter frit in a nitrogen purged dry box and washed withtwo-50 ml portion benzene. The residue was vacuum dried for 1 hour atambient temperature at 5 × 10⁻² mm Hg vacuum. The dried anchored rhodiumcomplex on cab-o-sil was submitted for C, H, Rh, P, Cl analysis. Found:C, 7.10; H, 0.93; Rh, 1.67; P, 0.95; Cl, 1.43; Calculated (as in (b)) C,5.93; H, 0.48; Rh, 1.73; P, 1.03, Cl, 4.23. (2) A portion of theanchored phosphine rhodium complex of (b) was Soxlet extracted withbenzene under a nitrogen purge for 19 hours. Following vacuum drying therhodium complex on cab-o-sil was submitted for C, H, Rh, P, Cl analysis.Found: C, 5.97; H, 0.70; Rh, 1.70; P, 1.03; Cl, 1.47.

This example demonstrates the retention of the anchored phosphinecomplex on the cab-o-sil surface under continuous benzene refluxing andheating with concentrated acetic acid at 150° C.

EXAMPLE 21 -- Mercurial Carbonylation Catalysis with Anchored Catalysts.

The reaction of organomercurials with carbon monoxide in the presence ofappropriate alcohol to form carboxylic acid derivatives was investigatedfor a series of anchored palladium and rhodium complexes. All reactionswere carried out in a 45 ml stainless steel Parr Reactor equipped formagnet stirring. The temperature of the Parr Reactor was maintainedconstant by suspension in a temperature regulated oil bath. Standardconditions for each catalyst run were: 4.0 mm phenylmercurictrifluoroacetate, 0.04 mm palladium or rhodium catalyst, 20 ml methanol,300 psig CO, 75° C., and 0.5 hr. reaction time. The conversion to methylbenzoate was determined by gas chromotography. The results are shown inTable IX.

The data show that the rate of reaction to form methyl benzoate wasstrongly dependent on the length of the anchoring chain. An increasefrom dimethylene to octamethylene bridge resulted in a threefoldincrease of conversion (Sequence Nos. 1 and 2). An increase of thecoordination number at the metal resulted in a decreased catalyticactivity. For example, L Pd(C₆ H₅ CN)PdCl₂ is more active than L₂ PdCl₂(Nos. 4 and 5). In both respects, the carbonylation of arylmercurycompounds is similar to the hydroformylation of olefins. However, forthe former reaction the mercury byproduct deactivates the anchoredcatalyst, while good activity maintenance is observed for olefinhydroformylation.

                                      TABLE IX                                    __________________________________________________________________________    Carbonylation of Phenylmercurictrifluoroacetate                               in the Presence of Methanol                                                   with Anchored Silylalkyl Phosphine                                            Rhodium and Palladium Complex Catalysts                                        ##STR23##                                                                    2C.sub.6 H.sub.5 CO.sub.2 CH.sub.3 + [HgOCOCF.sub.3 ].sub.2                                    Transition Metal Compound                                           Sequence No. in                                                                         Anchored Phosphine Complex                                                                      Yield, Methyl                                     Table V and Table                                                                       Disregarding HCl Elimination                                                                    Benzoate                                   Sequence No.                                                                         VI        on Anchoring      %                                          __________________________________________________________________________    1      2(V)      [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2) SiCl.sub.3 ].sub.2                       Rh(CO)Cl           6                                         2      4(V)      [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3                         ].sub.2 Rh(CO)Cl  20                                         3      1(VI)     (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3                          Pd(AcAc).sub.2    12                                         4      2(VI)     [(C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl].sub.2                        PdCl.sub.2        20                                         5      3(VI)     (C.sub.6 H.sub.5).sub.2 P(CH.sub.2).sub.8 SiCl.sub.3                          Pd(C.sub.6 H.sub.5 CN)Cl.sub.2                                                                  30                                         __________________________________________________________________________

EXAMPLE 22 -- Catalysis of Hexene Hydroformylation by AnchoredPhosphine-Cobalt Complexes

The chlorosilylated phosphine (2.17 g, 5 mm) was dissolved in 35 ml ofbenzene and added slowly with manual mixing to 5 grams (7.5 mmequivalents of silanol) of the cab-o-sil was then transferred to thedessicator-type vessel and transferred under nitrogen to thehigh-vac-line. The benzene was then removed at room temperature invacuo; the residue was kept at a pressure of 10⁻⁴ mm for 12 hours. Theresidual impregnated cab-o-sil was warmed in about 15 minutes to 100° C.At about 80° C. the pressure in the vacuum system increased indicatingthe evolution of the HCl by-product of the anchoring reaction. Heatingwas continued at 100° C. for 24 hours. Chlorine analysis of the abovetreated cab-o-sil gave 4.07% chlorine. The expected quantity of chlorinebased on the unreacted phosphine was 14.9%. Therefore, one-third of thechlorosilyl groups of the phosphine must have reacted with the silanolgroups of cab-o-sil.

EXAMPLE 23 -- Preparation of the Cobalt Carbonyl Complex ofβ-(Trichlorosilyl) Ethyl Diphenyl Phosphine ##STR24##

6.35 g (18.6 mm) of Co₂ (CO) was slurried in 80 ml of benzene in a 500ml round bottom flask. Then 9.5 g (37.3 mm) of the phosphine in 50 ml ofbenzene was added in small aliquots to the above mixture. During theaddition, a vigorous evolution of carbon monoxide was observed. Afterthe addition the heterogeneous mixture was refluxed for an additionalfour hours. The flask was stoppered and allowed to stand overnight. Themixture was filtered with suction using a 10-20 μ funnel to remove theunreacted cobalt carbonyl. The residue was washed with benzene and 5 mlof hexane. The combined filtrates were stripped of solvent using aroto-vac to obtain the yellow crystalline residual product. The infraredspectrum (IR) of the complex showed only carbonyl bands expected for anCo₂ (CO)₆ L₂ complex at 2025, 1985, and 1960 cm⁻¹.

Analyses calculated for C₃₄ H₂₈ P₂ Si₂ Cl₆ O₆ Co₂ : C, 41.64; H, 2.85;P, 6.22; Co, 12.03. Found: C, 36.47; H, 2.57; P, 5.77.

EXAMPLE 24 -- Preparation of the Cobalt Carbonyl Complex ofBis-[β-(Trichlorosilyl)] Ethyl Phenyl Phosphine ##STR25##

5.95 g (17.3 mm) of Co₂ (CO)₈ was added to 80 ml of benzene in a 500 mlround bottom flask equipped with a magnetic stirrer. Then 15 g (34.7 mm)of the phosphine were reacted in the manner described in the previousexample. A yellow-brown crystalline product was obtained. An IR analysisof the product gave the expected carbonyl stretching frequencies for anCo₂ (CO)₆ L₂ complex at 2020; 1990, and 1960 cm⁻¹. The nmr analysisshowed the expected α-methylene splitting pattern of the phosphinecomplex.

Analyses: Calculated for C₂₆ H₂₆ P₂ Si₄ Cl₂ C₆ Co₂ : C, 27.11; H, 2.26;P, 5.30; Co, 10.24. Found: C, 25.24; H, 2.29; P, 5.05.

EXAMPLE 25 -- Reaction of Anchored Cobalt-Carbonyl Phosphine Complexwith 1-Hexene and Water

20 ml 1-hexene (18 mm) and 3.24 ml H₂ O (18 mm) and enoughtetrahydrofuran to make the mixture homogeneous were placed in a reactorvessel equipped with a side arm and teflon stopcock. In the dry box 1.4g of supported cobalt carbonyl phosphine complex of Table VI, SequeneNo. 4 was added to the mixture. The reaction vessel was then closed andheated at 100° C. for 14 hrs. The vessel was then allowed to cool and asample for g.c. analysis was taken under a nitrogen purge. The anchoredcatalyst had not undergone any visible change under the above reactionconditions. The g.c. spectrum of the above reaction solution indicatedthe absence of alcohols, but indicated isomerization of the 1-hexene.The closed reaction vessel was then allowed to react for 3 hrs. at 200°C. The anchored cobalt phosphine carbonyl underwent a gradual visiblechange from light tan to silver during the heating. The vessel wasallowed to cool and a sample for g.c. analysis was taken again undernitrogen purge. The g.c. spectrum of the above solution showed nodifferences compared to that of the 100° C. reaction condition.

Analysis of anchored catalyst following above reaction: Calculated: P,3.08. Found: P, 1.81. Analysis of the liquid product mixture forphosphorus gave a value of 110 ppm.

EXAMPLE 26 -- Oxo-Type Reaction of 1-Hexene Catalyzed by the AnchoredCatalyst ##STR26##

Into a rocking autoclave were placed 1.5 g of the anchored catalyst ofTable VI, Seq. No. 4 and 20 ml of 1-hexene reactant together with 15 mlcyclohexane solvent. This resulted in a reaction mixture containing 1millimole of catalyst per mole of olefin. The autoclave was thenpressured up to 3000 lbs. per in² pressure with a 2 to 1 pressure ratioof hydrogen and carbon monoxide co-reactants. The temperature was thenraised to 200° C. wherein a sharp drop in the pressure indicated that anextremely rapid reaction has occurred. In 15 minutes about 92% of thehexene was converted. Six percent of the reacted olefin washydrogenated. The rest yielded oxygenated oxo-type products. Theoxo-product mixture had a 95 to 5 aldehyde to alcohol ratio and 55%product linearity according to analyses by gas liquid chromatography.

Analysis of the liquid product mixture for phosphorus gave a value lessthan 20 ppm. Infrared spectroscopy of the carbonyl region indicated thepresence of only trace quantities of cobalt carbonyl or cobalt carbonylphoshine complex. Analysis of anchored catalyst following abovereaction: Calculated: P, 3.08, Co, 5.95. Found: P, 1.91, Co, 6.85.

What is claimed is:
 1. Silylhydrocarbyl phosphine transition metalcomplexes of the formula:

    [(R'.sub.3-x P).sub.z Q.sub.y SiR.sub.4--y ].sub.g •(MX.sub.n).sub.s

wherein R is selected from the group consisting of chloro, C₁ -C₄acyloxy and C₁ -C₆ hydrocarbyl provided that at least one of the groupsis not hydrocarbyl, Q is (CH₂)_(p), p being 8 to 30, M is a transitionmetal of Group VI to VIII, X is an anion or organic ligand, R' isselected from the group consisting of C₁ -C₃₀ alkyl, cyclohexyl andphenyl, x is 1 to 3, y and z are 1 or 2, g is 1 to 6, s is 1 to 3 and nis 2 to
 6. 2. The complexes of claim 1 wherein R is chloro, Q is(CH₂)_(p) wherein p is 8 to 14, and R' is a C₁ -C₆ hydrocarbyl.
 3. Thecomplexes of claim 9 wherein R' is a C₁ -C₆ hydrocarbyl selected fromthe group consisting of saturated alkyl and aryl.
 4. The complexes ofclaim 1 wherein M is a Group VIII transition metal.
 5. The complexes ofclaim 3 wherein M is a Group VIII transition metal.
 6. The complexes ofclaim 1 wherein X is selected from the group consisting of chloride,bromide, and acetate and organic ligands selected from the groupconsisting of 1,5 cyclo-octadiene, carbonyl, tetrahydrofuran, pyridine,acetonitrile, 1,5,9 cyclododecatriene.
 7. The complexes of claim 1wherein R is selected from the group consisting of methyl, phenyl,chlorine, C₁ -C₄ acyloxy.
 8. The complexes of claim 6 wherein thetransition metal is of Group VIII.
 9. Silylhydrocarbyl phosphinetransition metal complex of the formula: ##STR27## wherein COD iscyclooctadiene.
 10. A method for the preparation of silylhydrocarbylphosphine transition metal complexes comprising the steps of:(a)selectively adding silanes of the formula

    R.sub.4-y SiH.sub.y

wherein R is selected from the group consisting of chlorine, C₁ -C₄acyloxy and C₁ -C₄ saturated aliphatic or aromatic hydrocarbyl providedthat at least one substituent is chlorine or C₁ -C₄ acyloxy, and y is 1or 2 to α - ω dienes of the formula:

    CH.sub.2 ═CH(CH.sub.2).sub.k CH═CH.sub.2

wherein k ranges from 1 to 26, at temperatures between -90° and +90° Cusing reactant ratios of 2 to 6 moles of diolefin per mole silane toform alkenyl silane adducts; (b) adding phosphines of the formula

    R'.sub.3-x PH.sub.x

wherein R' is selected from the group consisting of C₁ -C₃₀ alkyl,cyclohexyl and phenyl and x is 1 to 3 to the alkenyl silane of theformula

    (R.sub.4-y Si[(CH.sub.2).sub.1 CH═CH.sub.2 ].sub.y )

of step (a) wherein R and y are as previously defined and 1 is k + 2, attemperatures between -100° and +16° C to form silylhydrocarbylphosphines; (c) complexing silylhydrocarbyl phosphines of the formula:

    (R'.sub.3-x P).sub.z [(CH.sub.2).sub.m ].sub.y SiR.sub.4-y

of step (b) wherein R, R' and x and y are as previously defined and z is1-3 and m is k + 4, with transition metal compounds of the formulaMX_(n), wherein M is a transition metal selected from the groupconsisting of Group VI, VII and VIII of the Periodic Table of theElements, X is an anion or organic ligand which satisfies thecoordination sites of the metal and n is 2 to 6, to formsilylhydrocarbyl phosphine transition metal complexes of the formula

    [(R'.sub.3-x P).sub.z (CH.sub.2).sub.m SiR.sub.4- ].sub.g •(MX.sub.n).sub.s

wherein R, R', M, X, n, m, y and z are as previously defined, g is 1 to6 and s is 1 to
 3. 11. The method of claim 10 wherein the transitionmetal compounds to be complexed are of Group VIII.
 12. The method ofclaim 10 wherein X is an anion selected from the group consisting ofchloride, bromide, acetate, and an monoolefins, diolefins,tetrahydrofuran, pyridine, acetonitrile and cyclododecatriene.
 13. Themethod of claim 10 wherein the reactive R group of the silane ischlorine.
 14. The method of claim 10 wherein the reactive R group of thesilane is acyloxy.
 15. The method of claim 10 wherein the R' group ofthe phosphine is C₁ -C₄ alkyl, cyclohexyl and phenyl.
 16. A method forthe preparation of silylhydrocarbyl phosphine transition metal complexescomprising the steps of:(a) selectively adding silanes of the formula

    R.sub.3 SiH

wherein R is chlorine to α, ω - dienes of the formula

    CH.sub.2 ═CH(CH.sub.2).sub.k CH═CH.sub.2

wherein k is 4 to 10, at temperatures between -90° and +90° C usingreactant ratios of 2 to 6 moles of diolefin per mole silane to formalkenyl silane monoadducts of the formula

    R.sub.3 Si(CH.sub.2).sub.1 CH═CH.sub.2

wherein 1 is k + 2; (b) adding phosphines of the formula

    R'.sub.2 PH

wherein R' is C₁ -C₃₀ alkyl, cycloalkyl and phenyl to the alkenyl silaneof (a) at temperatures between -100° and +16° C to form silylhydrocarbylphosphines of the formula

    R.sub.3 Si(CH.sub.2).sub.m PR'.sub.2

wherein m is K + 4; (c) complexing the silylhydrocarbyl phosphine of (b)to Group VIII transition metal compounds of the formula

    MX.sub.n

wherein M is the transition metal, X is an anion selected from the groupconsisting of chloride, bromide, acetate and organic ligand selectedfrom the group consisting of carbonyl, tetrahydrofuran, pyridine,acetonitrile and 1,5 cyclooctadiene, n is 2 to 6, to form complexes ofthe formula

    [R.sub.3 Si(CH.sub.2).sub.m PR'.sub.2 ].sub.g •(MX.sub.n).sub.s

wherein g is 1 to 6 and s is 1 to 3.